Introduction of Nitrogen into uranium and thorium halides: Reactions with liquid ammonia, amides, imides, nitrides, and azides

铀和钍的化学性质是众所周知的-在处理核目的的部分，如元素的分离，同位素分离或核燃料的处理。除了这些核主题之外，知识是稀缺的。在我们的项目中，我们希望远离这些核目的，专注于铀和钍的基本化学。铀和钍卤化物的化学反应，特别是氟化物的化学反应，有待进一步探讨。我们的主要兴趣是合成含氟和氮的化合物，如氟胺，以及混合阴离子化合物，如氟酰胺，酰亚胺和相应的氮化物。氮将使用氨、肼、酰胺、酰亚胺、氮化物和叠氮化物，使用固态技术以及在液氨溶液中的溶液技术引入。据我们所知，除了少数几个例子外，这种化合物是未知的。然而，由于它们应该在结构上与氧化物相关，因此化合物应该具有有趣且相似的可用磁性，光学和电子特性。近年来，混合阴离子化合物变得越来越重要，例如发现了超导氟化物氧化物。氮化物在工业上用作硬质材料、耐高温物质，但也用作LED中的发光体。通常氮化物在高温和/或高压下合成。在我们的项目中，我们希望开发一种基于卤化物在液氨中连续氨解的低温氮化物路线。我们在第一个提案中的初步工作非常成功：除了几种新化合物外，与铀，钍和氟化学的接触使我们能够发现并解决一个近200年的争议：只有利用第一个提议中获得的知识，我们才能明确地证明自然界中元素氟的存在。

The chemistry of uranium and thorium is well known - in sections dealing for nuclear purposes such as isolation of the elements, isotope separation, or workup of nuclear fuels. Besides these nuclear topics the knowledge is scarce.With our project we would like to stay away from such nuclear purposes and focus on the basic chemistry of uranium and thorium. The chemical reactions of uranium and thorium halides, with a special emphasis on those of the fluorides, are to be explored further. Our main interest is the synthesis of fluorine and nitrogen containing compounds like fluoride ammines, but also mixed-anionic compounds like fluoride amides, imides, and the respective nitrides. Nitrogen is to be introduced using ammonia, hydrazine, amides, imides, nitrides, and azides using solid state techniques as well as solution techniques in liquid ammonia solution. To the best of our knowledge such compounds are - except for a few examples - unknown. However, as they should be structurally related to oxides, the compounds should feature interesting and similar usable magnetic, optic, and electronic properties. In recent years mixed-anionic compounds have become more important, as for example superconducting fluoride oxides have been discovered.Nitrides are industrially used as hard materials, high temperature resistant substances, but also as light emitters in LEDs. Usually nitrides are synthesized at high temperatures and/or pressures. In our project we would like to develop a low temperature route to nitrides based on successive ammonolysis of halides in liquid ammonia.Our preliminary work during the first proposal was very successful: Besides a couple of novel compounds, the engagement with uranium, thorium, and fluorine chemistry allowed us to spot and settle an almost 200 year old dispute: Only with the knowledge gained in the first proposal we could unambiguosly proof the existence of elemental fluorine in nature.